How Ions Break Local Symmetry: Simulations of Polarized Transient Hole Burning for Different Models of the Hydrated Electron in Contact Pairs with Na.

The hydrated electron (e) is known via polarized transient hole-burning (pTHB) experiments to have a homogeneously broadened absorption spectrum. Here, we explore via quantum simulation how the pTHB spectroscopy of different e models changes in the presence of electrolytes. The idea is that cation-e pairing can break the local symmetry and, thus, induce persistent inhomogeneity. We find that a "hard" cavity model shows a modest increase in the pTHB recovery time in the presence of salt, while a "soft" cavity model remains homogeneously broadened independent of the salt concentration. We also explore the orientational anisotropy of a fully density functional theory-based model of the e, which is strongly inhomogeneously broadened without salt and which becomes significantly more inhomogeneously broadened in the presence of salt. The results provide a direct prediction for experiments that can distinguish between different models and, thus, help pin down the hydration structure and dynamics of the e.